Nitro dyestuffs

ABSTRACT

THIS INVENTION RELATES TO DISPERSE DYES OF THE NITRO SERIES WHICH ARE SUBSTITUTED BY A RADICAL OF FORMULA   -O-CH2-O-CH2-   AND ARE VERY SUITABLE FOR DYEING AND PRINTING OF FIBRES AND FIBRE MATERIALS MADE OF FULLY SYNTHETIC OR SEMISYNTHETHIC, HYDROPHOBIC, HIGH MOLECULAR ORGANIC SUBSTANCES.

United States Patent 3,637,669 NITRO DYESTUFFS Ruedi Altermatt,Tecknau-Basel, Switzerland, assignor to Sandoz Ltd. (also known asSandoz A.G.), Basel, Switzerland No Drawing. Filed Oct. 28, 1968, Ser.No. 771,372 Claims priority, application Switzerland, Nov. 17, 1967,16,140/ 67 Int. Cl. (307d 15/04 US. Cl. 260-239.6 10 Claims ABSTRACT OFTHE DISCLOSURE This invention relates to disperse dyes of the nitroseries which are substituted by a radical of formula OCH -OCH and arevery suitable for dyeing and printing of fibres and fibre materials madeof fully synthetic or semisynthetic, hydrophobic, high molecular organicsubstances.

The new dyes are of the formula wherein R stands for a hydrogen orhalogen atom or a hydroxyl, nitro, cyano, alkyl, alkoxy, phenoxy,acylamino or acyl group of together with R for a bridge member of theformula -OCH -O'CH R for a hydrogen or halogen atom or a cyano, nitro,alkyl, alkoxy, phenoxy, acyl or acylamino group, or together with R fora bridge member of the formula R for a halogen atom or a cyano, nitro oracyl group or a radical of the formula R for a hydrogen or hydrogen atomor an alkyl, alkoxy, acylamino or carboxylic acid ester group ortogether with R for a bridge member of the formula R for a hydrogen atomtogether with R for a bridge member of the formula -CH OCH O-, and

Y for a group of the formula CO- or SO at least one of the nuclei A andB is substituted by a group of the formula CH -OCH -O- and the moleculemay bear further substituents with the exception of sulphonic acidgroups.

The acyl groups may be of the formula R'X or "-W- where R' stands for ahydrocarbon radical which may bear non-water-solubilizing substituentsand/ or hetero atoms, preferably an optionally substituted alkyl orphenyl radical such as the aforementioned, X for a radical of theformula -OCO or SO R" for a hydrogen atom, cycylohexyl or 'R', W for aradical of the formula CO-, NR"CO or and R for a hydrogen atoms or R.

Examples of preferred substituents on the bridge members of the formulaOCH O-CH are methyl or trichloromethyl radicals.

A number of the preferred dyes of this invention are of the formula I Io NHR10 l N02 Br 3 0 RB (III) where R stands for a hydrogen, chlorine orbromine atom or an alkyl group; R for a hydrogen, chlorine or bromineatom or an alkyl or alkoxy group; R and R independently of each other,for a hydrogen atom or an alkyl group which may be substituted byfluorine, chlorine or bromine atoms; and R for a chlorine or bromineatom or a cyano, nitro, alkylcarbonyl, alkoxycarbonyl, benzoyl,aminocarbonyl, alkylsulphonyl, phenylsulphonyl or aminosulphonyl group;the alkyl groups may all be substituted by chorine or bromine atoms,hydroxy, alkoxy, phenyl, phenyloxy or cyano groups, the phenyl radicalsmay be substituted by chlorine or bromine atoms, alkyl, alkoxy, nitro,cyano, acylamino phenyl or phenyloxy groups, and the amino groups byalkyl or phenyl radicals.

Other preferred dyes are of the formula Where R R R and R have theaforestated meanings; R stands for a hydrogen, chlorine or bromine atomor an alkyl group; R for a hydrogen, chlorine or bromine atom or analkyl group; R for a hydrogen or halogen atom, a nitro, cyano, alkoxy,acylamino or carboxylic acid ester group or, together with R for abridge member of the formula n a (V) and R for a hydrogen or halogenatom or a hydroxyl, alkyl, alkoxy, cyano, nitro, alkylcarbonyl,alkylsulphonyl, phenylmethylsulphonyl, phenylethylsulphonyl,alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl, aminocarbonyl,acylamino or aminosulphonyl group or, together with R for a group ofFormula V; the alkyl groups may be substituted by chlorine or bromineatoms, hydroXyl, alkoxy, phenoxy or cyano groups, the phenyl groups byhalogen atoms, cyano, nitro, alkyl, alkoxy, phenyl or phenyloxy groups,and the amino groups by alkyl or phenyl radicals.

The new dyes of Formula I are produced by reacting an amine of theformula with a compound of the formula Hal- R;

1 (VII) where Hal represents a chlorine or bromine atom.

The reaction of a compound of Formula VI with a compound of Formula VIIis generally effected in the temperature range of to 200 C., dependingon the reactivity of the halogen atom, either in water or in an organicsolvent e.g. ethanol, n-butanol, benzylalcohol, ethylene glycol,polyethylene glycol, benzene, toluene, etc. It is usually of advantageto add an acid-binding agent to the reaction mixture, e.g. sodiumacetate, sodium carbonate or bicarbonate, or magnesium oxide.

Compounds of Formula I in which R represents a radical of Formula II areobtainable by reacting 1 mole of a compound of the formula Hal -Y-Hal 1102 (VIII) with 1 mole of an amine of the formula H NQIQ R5 (IX) andthen reacting the product with 1 mole of an amine of Formula VI. Thereaction conditions are generally the same as given in the foregoing.

Compounds of Formula I in which R is a radical of Formula H canalternatively be produced by reacting 1 mole of a compound of theformula with 1 mole of an amine of Formula VI, e.g. under theaforestated conditions, halogenating the resulting compound to acompound of the formula I R; No; (XI) and reacting this compound with anamine of Formula IX, again under the aforestated conditions.

Halogenation is carried out preferably in an inert solvent, e.g. carbontetrachloride or carbon disulphide, using either phosphorus trichlorideor, in the absence of solvent, thionyl chloride.

It is desirable to convert the new dyes into dye preparations beforeuse, using for this purpose one of the known methods, for examplegrinding in the presence of dispersing agents and/or fillers, withsubsequent drying. On the addition of a suitable volume of water the dyepreparations can be applied to the fibre by exhaustion dyeing, paddyeing or printing methods.

From aqueous dispersion the dyes build up excellently on semi-syntheticand synthetic fibres of hydrophobic character and high molecular weight.They are particularly suitable for the exhaustion dyeing, pad dyeing andprinting of linear aromatic polyester, cellulose diacetate,

cellulose triacetate and polyamide fibres. Polyolefine fibres also aredyeable with these dyes.

The known dyeing and printing methods are employed, for example thatdescribed in French Pat. 1,445,371. The dyeings and prints obtained areof yellow shade and have very good fastness properties, beingoutstandingly fast to thermo-fixation, sublimation, pleating, ozone andgas fumes. The fastness to water, perspiration, washing and other wettests is also very good; the reserve of Wool and the light fastness arenotable. The dyes are stable to the action of the different forms ofpermanent press finishing. They are stable to boiling and reduction attemperatures up to about 220 C. and particularly to 140 C., andwithstand a wide range of acids and alkalis. These stability propertiesare not adversely affected by the liquor ratio or by the pr :sence ofdyeing accelerants. The dyeings and prints are not subject to catalyticfading to any appreciable degree, but fade tone-in-tone on exposure tolight. In the following examples the parts are by weight and thetemperatures in degrees centigrade.

EXAMPLE 1 A mixture of 15.1 parts of 6-amino-1,3-benzodioxine, 31.3parts of 1-chloro-2-nitrobenzene-4-sulphonic acid phenylamide, parts ofethylene glycol and 9.2 parts of anhydrous sodium acetate is raised toin 30 minutes with vigorous stirring and stirred further for 30 minutesat 130-135", on which it is allowed to cool to about 70 as it is thendifficult to stir. At the latter temperature it is diluted with 80 partsof methanol, and the dye formed is filtered off, washed with a littlemethanol and then with water, and finally dried. This dye gives dyeingsof yellow shade on synthetic fibres which have excellent fastnessproperties.

EXAMPLE 2 A mixture of 9.3 parts of aminobenzene, 37 parts of thecompound of the formula 200 parts of ethylene glycol and 9.2 parts ofanhydrous sodium acetate is raised over 30 minutes to 130 with thoroughstirring and is stirred further at 130-135 for 30 minutes. After thistime the mixture is allowed to cool to room temperature, at which thedye settles out in the form of fine needles. It is filtered off, washedwith a little ethanol and then with water and dried. The dye thusobtained dyes synthetic fibres in yellow shades having excellentfastness properties.

EXAMPLE 3 A mixture of 25.6 parts of 1-chloro-2-nitrobenzene-4-sulphonic acid chloride, 30.2 parts of 6-amino-1,3-benzodioxine, 120parts of ethylene glycol and 20 parts of anhydrous sodium acetate isbrought to 40 over 30 minutes and'over the next 30 minutes thetemperature is increased to ISO-. The reaction mixture is then allowedto cool to 70, diluted with 100 parts of ethanol and allowed to coolfurther to room temperature. The dye settles out and is filtered off,washed with a little ethanol and then with hot water and dried. Onsynthetic fibres this dye gives dyeings of yellow shade and excellentfastness.

The dyes set out in the following table can be produced in accordancewith the procedures given above. They are of the formula Shade onpolyester Example N o. A R fibre 30 01 Yellow.

0- l CH S ONE 0 Hg /CH1 OHz-O 31 0 -SOzNHCHzCHzCHaOCHa Do.

O-CH2 32 Same as above CH Do.

34 Same as above Do.

0 S O2-N i OCH2 36 Same as above SO2NH -CH;

38 ..do CH;

CHzCHzCN 39 .-d0 C ON(CH2CH:CN)1

01 S02NE O 42 Same as above Do.

43 V o Do.

CHaO

45 0 ...d0 Do.

46 "do Do.

4s Do.

CH3 S 02- 0- -S OzNH- Shade on polyester Example No. A R fibre 65 0 /CHYellow.

S Oz-N C-CH CH;

CH2 0 O--CH2 66 CoHs- ('31 D0.

S O2NH- O\ /CII2 CHz-O G7 Same as above 0 CH; Do.

S OzNH- O /CH: CH2O 9- s OzNH o Cl /CH2 CHa-O 69 Q Same as above Do.

0 O O CH:

71 -Br Do.

O-CH2 72 Same as above DJ.

75 --do s zN -C Br Do.

76 "do s own-Cw CH: D0.

77 "do s (mm-@402 D0.

78 .410 s cam-O-cr Do.

so .do s cam-O-o-O CHz-O Same as above s2 GENO-O Do Representativedyestuffs of the foregoing examples are as follows CE; l7

Example 1 I NO;

Hz-O Example 2 /0 E i NO O-- H3 2 Example 57 Having thus discussed theinvention, what I claim is: 1. Disperse dye free from sulphonic acidgroups and of the formula R; N 02 wherein R is a hydrogen atom, halo,hydroxy, nitro, cyano, alkyl, alkoxy, phenoxy, acetoxy, phenoxyacetoxy,chloro benzoyloxy, nitrobenzoyloxy, acyl, acylamino or, together with Ra bridge member of the formula l a a -00Ho-( JH- R is a hydrogen atom,halo, cyano, nitro, alkyl, alkoxy,

phenoxy, acyl, acylamino or, together with R a bridge member of theformula R is halo, cyano, nitro, acyl or a radical of the formula R; isa hydrogen atom, halo, alkyl, alkoxy, acylamino, alkoxycarbonyl or,together with R a bridge member of the formula R is a hydrogen atom or,together with R a bridge member of the formula each of R and R is,independently, a member selected from the group consisting of a hydro-18 gen atom, alkyl, fluoroalkyl, chloroalkyl and bromoalkyl; Y is CO- orSO each acyl being of one of the formulae R'-X and R"-- wherein R isphenyl or alkyl;

R" is a hydrogen atom, phenyl, alkyl or cyclohexyl; W is CO-, -NR"CO- orNR""SO R' is a hydrogen atom, phenyl or alkyl;

each alkyl and each alkoxy containing 1, 2, 3 or 4 carbons; any furthersubstituent on an alkyl or alkoxy being a member selected from the groupconsisting of halo, hydroxy, cyano, alkoxy, phenyl, phenoxy, acyl andacyloxy; any further substituent on a phenyl nucleus being a memberselected from the group consisting of halo, hydroxy, alkyl, alkoxy,phenyl, phenoxy, cyano, nitro, acyl, acyloxy and acylamino; any furthersubstituent on an amino nitrogen being alkyl or phenyl; and the dyecontaining at least one of the nuclei A and B substituted by a group ofthe formula R8 R9 -iJHo-i1Ho- 2. Disperse dye of the nitro seriesaccording to claim 1 and of the formula RnCH I N0, o---- H Rs (III)wherein R is a hydrogen atom, chloro, bromo or alkyl;

R, is a hydrogen atom, chloro, bromo, alkyl or alkoxy;

and

R is chloro, bromo, cyano, nitro, alkylcarbonyl, alkoxycarbonyl,benzoyl, aminocarbonyl, alkylsulphonyl, phenylsulphonyl oraminosulphonyl;

any further substituent on an alkyl being a member selected from thegroup consisting of chloro, bromo, hydroxy, alkoxy, phenyl, phenoxy andcyano; and any further substituent on a phenyl nucleus being a memberselected from the group consisting of chloro, bromo, alkyl, alkoxy,nitro, cyano, acylamino, phenyl and phenoxy.

3. Disperse dye of the nitro series according to claim 1 and of the[formula 0 R1 R12 u R14 NHYNH o 11:02 i CH-R HO 1 (Iv) whereincar-bonyl, acylamino, aminosulphonyl or, together with R13, a bridgemember of the formula R R, O EH O EH any further substituent on an alkylbeing a member selected from the group consisting of cholro, bromo,hydroxy, alkoxy, phenoxy and cyano; and any further substituent on aphenyl nucleus being a member selected from the group consisting ofhalo, cyano, nitro, alkyl, alkoxy, phenyl and phenoxy.

4. Disperse dye of the nitro series according to cla 1 wherein R is aradical of the formula and Y is SO 5. Disperse dye of the nitro seriesaccording to claim 1 wherein R is a radical of the formula B (II) and Yis CO.

6. The dye according to claim 1 of the formula 7. The dye according toclaim 1 of the formula I N O 2 8. The dye according to claim 1 of theformula I NO;

OCH 11 -0 9. The dye according to claim 1 of the formula 10. The dyeaccording to claim 1 of the formula THENRY R. JILES, Primary Examiner*C. M. SHURKO, Assistant Examiner US. Cl. X.R.

if 1E3 UTGI ED STATES PATENT @FFICE CERTIFICATE 0F CURECHCN Patent No.3,637,669 Dated January 25, 1972 I RUEDI ALTERMATT It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Column 1, line 25, in the formula, "R should read -R "(1)" should read(I) line 31, "of" should read -or-; line 37, after the formula, 7 inserta comma line 44, after the formula, "(II)" should read (II) lines 52 to56, "Y acid groups." should read:

Y for a group of the formula CO- or '-SO at least one of the nuclei Aand B is substituted by a group of the formula CH O-CH 0- and themolecule may bear further substituents with the exception of sulphonicacids groups.; line 61, "alkoxy" should read alkoxy,-. Column 2, line10, "-SO should read S0 line 27, "R should read --R line 34, "chorine"should read chlorine-; line 37, "acylamino" should read --acylamino,;line 56,

in the formula, "R (first occure nce) should read --R line 63, "V;"should read (V) Column 3, line 13, after the formula, "(VII should read(VII); line 15, "VI" should read (VI)-; line 16, "Vll" should read-(VII); line 24, "I" should read -(I)- line 25, "II" should read--(II)-; line 39, '"VI." should read-(VI).; line 41, "I" should read(I)-; line 42, "II" should read -(II)-; line 49, "VI," should read(VI),-; line 57, "IX," should read -(IX),-. Column 4, line 18, start anew paragraph with "In the"; line 42, after the formula, insert a commaColumn 8, Example 30, in the definition of R, delete "Cl". Column 9Example id 56, in the definition of A, "W should read W" Column 12,Example 65,

CH CH in the definition of R, "C-CH" should read --CCH Example 67 .inthe definition of R, "SO NH" should read -S0 NH Column 13, Example 103,

"03" should read --lO3--. Column 15, Example 113, in the definition ofA,

should read Column 17, line 32, "discussed' shoulia mg UNITEDSTATES-PATENT Wm;

' CERTIFICATE OF CRECHQN Patent No. 3,637,669 Dated January 25, 1972Inventor-(s) RUEDI ALTERMATT It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

r ead disclosed-; line 42, "chloro" should read chloroline 46, w

after the formula, insert a semicolon line 54, after the formula, inserta semicolon line 60, after the formula, "(II)" should read (II) line 66,after the formula, inserta semicolon line 72, in the formula, "and"should read and-;. Column 18, line 26, after the formula, insert aperiod line 70, after the formula, insert a semicolon Column 19, line 3,after the formula, insert a semicolon line 34, "-SO ONH-'-" should readSO'NH- line 20,

2 2 "-0" should read Cl.

Signed and sealed this 6th day of March 1973.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTT SCHALK Attesting Officer Commissionerof Patents

